US3639540A - Sulfinyl phenyl esters of thionophosphoric or thionophosphonic acids - Google Patents
Sulfinyl phenyl esters of thionophosphoric or thionophosphonic acids Download PDFInfo
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- US3639540A US3639540A US780870A US3639540DA US3639540A US 3639540 A US3639540 A US 3639540A US 780870 A US780870 A US 780870A US 3639540D A US3639540D A US 3639540DA US 3639540 A US3639540 A US 3639540A
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- -1 Sulfinyl phenyl esters Chemical class 0.000 title abstract description 22
- 239000002253 acid Substances 0.000 title abstract description 10
- 150000007513 acids Chemical class 0.000 title 1
- 239000000642 acaricide Substances 0.000 abstract description 2
- 239000002917 insecticide Substances 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 239000000460 chlorine Substances 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 18
- 229910052801 chlorine Inorganic materials 0.000 description 17
- 239000000203 mixture Substances 0.000 description 15
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000000361 pesticidal effect Effects 0.000 description 8
- 229940073584 methylene chloride Drugs 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- GBDZXPJXOMHESU-UHFFFAOYSA-N 1,2,3,4-tetrachlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1Cl GBDZXPJXOMHESU-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 206010004194 Bed bug infestation Diseases 0.000 description 4
- 241001674044 Blattodea Species 0.000 description 4
- 241001414835 Cimicidae Species 0.000 description 4
- 241000254171 Curculionidae Species 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 241000344246 Tetranychus cinnabarinus Species 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010410 dusting Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- UERPKMLSSINZIO-UHFFFAOYSA-M sodium 2,5-dichloro-4-methylsulfinylphenolate Chemical compound ClC1=C(C=C(C(=C1)S(=O)C)Cl)[O-].[Na+] UERPKMLSSINZIO-UHFFFAOYSA-M 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical compound OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 238000010517 secondary reaction Methods 0.000 description 2
- MVUHDEFEIKWDGU-UHFFFAOYSA-N 1,2,3-trichloro-4-methylsulfanylbenzene Chemical compound CSC1=CC=C(Cl)C(Cl)=C1Cl MVUHDEFEIKWDGU-UHFFFAOYSA-N 0.000 description 1
- JHBKHLUZVFWLAG-UHFFFAOYSA-N 1,2,4,5-tetrachlorobenzene Chemical compound ClC1=CC(Cl)=C(Cl)C=C1Cl JHBKHLUZVFWLAG-UHFFFAOYSA-N 0.000 description 1
- IQZDYLLNDXHENI-UHFFFAOYSA-N 1,2,4-trichloro-3-methylsulfanylbenzene Chemical compound CSC1=C(Cl)C=CC(Cl)=C1Cl IQZDYLLNDXHENI-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- DUCFPRCCKPCKPB-UHFFFAOYSA-N 3,4-dichloro-2-methylsulfinylphenol Chemical compound CS(=O)C1=C(C=CC(=C1Cl)Cl)O DUCFPRCCKPCKPB-UHFFFAOYSA-N 0.000 description 1
- 125000004189 3,4-dichlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(Cl)C([H])=C1* 0.000 description 1
- FWVDIIXTWCBWCI-UHFFFAOYSA-N 4,5-dichloro-1-methylsulfanylcyclohexa-2,4-dien-1-ol Chemical compound CSC1(CC(=C(C=C1)Cl)Cl)O FWVDIIXTWCBWCI-UHFFFAOYSA-N 0.000 description 1
- SCCWFINJWKIRDD-UHFFFAOYSA-N 6-sulfinylcyclohexa-2,4-dien-1-ol Chemical compound OC1C=CC=CC1=S=O SCCWFINJWKIRDD-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241001124076 Aphididae Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- HZBFWRKXQNPMER-UHFFFAOYSA-N C(C)P(=S)(Cl)[ClH]CC Chemical compound C(C)P(=S)(Cl)[ClH]CC HZBFWRKXQNPMER-UHFFFAOYSA-N 0.000 description 1
- DHNJJLGNNQXPRZ-UHFFFAOYSA-N C(C)[ClH]P(=S)(Cl)[ClH]CC Chemical compound C(C)[ClH]P(=S)(Cl)[ClH]CC DHNJJLGNNQXPRZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241001327638 Cimex lectularius Species 0.000 description 1
- WJXGTMBHOPEHGM-UHFFFAOYSA-N Cl.CCOP(C)(O)=S Chemical compound Cl.CCOP(C)(O)=S WJXGTMBHOPEHGM-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000257159 Musca domestica Species 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 241001454293 Tetranychus urticae Species 0.000 description 1
- CXDBXTHJTZQPOJ-UHFFFAOYSA-M [Na+].CC=C.CC=C.CC=C.CC=C.[O-]S(=O)(=O)C1=CC=CC=C1 Chemical compound [Na+].CC=C.CC=C.CC=C.CC=C.[O-]S(=O)(=O)C1=CC=CC=C1 CXDBXTHJTZQPOJ-UHFFFAOYSA-M 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Chemical group 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- HAMPFDSXJDAQQU-UHFFFAOYSA-N ethoxy-ethyl-hydroxy-sulfanylidene-lambda5-phosphane hydrochloride Chemical compound Cl.CCOP(O)(=S)CC HAMPFDSXJDAQQU-UHFFFAOYSA-N 0.000 description 1
- SHHNZMWZZCIDHE-UHFFFAOYSA-N ethoxy-hydroxy-phenyl-sulfanylidene-lambda5-phosphane hydrochloride Chemical compound Cl.CCOP(O)(=S)C1=CC=CC=C1 SHHNZMWZZCIDHE-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000015250 liver sausages Nutrition 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/18—Esters of thiophosphoric acids with hydroxyaryl compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having alternatively specified atoms bound to the phosphorus atom and not covered by a single one of groups A01N57/10, A01N57/18, A01N57/26, A01N57/34
- A01N57/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having alternatively specified atoms bound to the phosphorus atom and not covered by a single one of groups A01N57/10, A01N57/18, A01N57/26, A01N57/34 containing aromatic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4084—Esters with hydroxyaryl compounds
Definitions
- This invention relates to novel esters of thionophosphoric acid or thionophosphonic acid, as well as to a method of preparing these compounds.
- the present invention relates to a novel class of compounds of the formula I wherein R is alkyl of 1 to 3 carbon atoms,
- R is alkyl of 1 to 3 carbon atoms, methoxy, ethoxy or phenyl, and v v R is alkyl of 1 to 4 carbon atoms.
- the compounds of the Formula I above may be prepared by a method involving well knownchemical principles, namely, by reacting a dichlorophenol of the formula WQSH.
- R has the same meanings as in Formula I, or a salt, especially an alkali metal salt, thereof with a halide of thionphosphoric acid or thionophosphonic acid of the formula wherein X is chlorine or bromine and R and R have the same meanings as in Formula I, in the presence of an inert solvent and an acid-binding agent at elevated temperatures.
- suitable solvents areorg'anic solvents, such as ketones, aromatic hydrocarbons, ethers and halogenated hydrocarbons, especially toluene, dioxane or methyl isobutyl ketone, or also water.
- the majority of the compounds according to the present invention are non-distillable oils, and a few are crystalline substances.
- the compounds are thin-layer chromatographically uniform, using as the flow agent a mixture of hexane and acetone (2:1), developed with a 3% palladium chloride solution.
- the dichlorophenols of the Formula II, used as starting compounds, may. be prepared by the. following method: Y
- a suitable, tetrachlorobenzene such as 1,2,3,4-tetrachlorobenzene, preferably in slight stoichiometric excess,
- the reaction product was a mixture of 76% of 1-methylmercapto-3,4-dichlorophenol and 24% of l-methylmercapto-3,6-dichlorophenol, as verified by NMR-spectrum and gas chromatographical analysis. For separation of the isomers a fractionating column was used.
- 2-methylsulfinyl-3,4-dichlorophenol was obtained from the corresponding Z-methylmercapto compound by oxidation with the molecular quantity of hydrogen peroxide in glacial acetic acid at 0 to 40 C. in conventional fashion. The phenol melted at 216-218 C.
- novel compounds according to the present invention are highly effective broad-spectrum pesticides; they act not only as contact poisons but also as alimentary canal poisons. Their toxicity toward warm-blooded animals is extremely low. They are particularly eflective against red spider mites, aphids, weevils( Calandra), bedbugs (Cimex lectularius), roaches and the common housefly.
- the compounds according to the present invention are disseminated in the form of compositions consisting essentially of an inert carrier and a pesticidally efiective amount of the active ingredient.
- the inert carrier may be a gaseous substance, such as a propellant gas, or a liquid or solid substance.
- the compositions may comprise one or more other inert additives, such as emulsifiers, extenders and substances which increase the adherence of the compositions to surfaces or objects to which they may be applied.
- the compounds of the present invention may be the sole active pesticidal ingredients in the compositions, or they may be combined with other pesticidal agents. Examples of suitable forms of such compositions are, among others: dusting powders, suspensions, emulsions, solutions, aerosols, fumigating paper or powder, and ointments.
- the preferred concentration of the compounds according to the present invention in such pesticidal compositions is from- 0.01 to 5% by weight.
- Emulsion 25 gm. of a compound of the Formula I, gm. of dimethylformamide and 5 gm. of nonylphenol polyglycol ether (emulsifier) were emulsified in an amount of water suflicient to make the concentration of the active ingredient from 0.01 to 0.2% -by weight, based on the overall weight of the emulsion.
- EXAMPLE 9 Dusting powder.5 gm. of a compound of the Formula I, 94 gm. of talcum and 1 gm. of methylcellulose were admixed and milled until a homogenous powder was obtained.
- the dusting powder comprising 5% of the pesticidal ingredient, was also very effective in combatting red spider mites, weevils, bedbugs and roaches.
- EXAMPLE 1 0 Suspension.-A mixture of 50 gm. of a compound of the Formula I, 9 gm. of lignin sulfonate (dispersing agent), 1 gm. of sodium tetrapropylene benzene sulfonate (wetting agent) and 40 gm. of kaolin was milled, and the resulting intimate mixture was suspended in an amount of water sufiicient to make the concentration of the active ingredient from 0.01 to 0.5% by weight, based on the overall weight of the suspension.
- lignin sulfonate dispersing agent
- wetting agent sodium tetrapropylene benzene sulfonate
- kaolin 40 gm. of kaolin
- the resulting pesticidal suspension was also highly effective against red spider mite, weevils, bedbugs and roaches.
- R is alkyl of 1 to 3 carbon atoms, methoxy, ethoxy or phenyl, and R is alkyl of 1 to 4 carbon atoms.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
SULFINYLPHENYL ESTERS OF THIONOPHOSPHORIC ACID OR THIONOPHOSPHONIC ACID AND ARE USEFUL AS INSECTICIDES AND ACARICIDES.
Description
United States Patent ABSTRACT OF THE DISCLOSURE Sulfinylphenyl esters of thionophosphoric acid or thionophosphonic acid and are useful as insecticides and acaricides.
This invention relates to novel esters of thionophosphoric acid or thionophosphonic acid, as well as to a method of preparing these compounds. I
More particularly, the present invention relates to a novel class of compounds of the formula I wherein R is alkyl of 1 to 3 carbon atoms,
R is alkyl of 1 to 3 carbon atoms, methoxy, ethoxy or phenyl, and v v R is alkyl of 1 to 4 carbon atoms.
The compounds of the Formula I above may be prepared by a method involving well knownchemical principles, namely, by reacting a dichlorophenol of the formula WQSH.
wherein R has the same meanings as in Formula I, or a salt, especially an alkali metal salt, thereof with a halide of thionphosphoric acid or thionophosphonic acid of the formula wherein X is chlorine or bromine and R and R have the same meanings as in Formula I, in the presence of an inert solvent and an acid-binding agent at elevated temperatures. Examples ofsuitable solvents areorg'anic solvents, such as ketones, aromatic hydrocarbons, ethers and halogenated hydrocarbons, especially toluene, dioxane or methyl isobutyl ketone, or also water.-
The majority of the compounds according to the present invention are non-distillable oils, and a few are crystalline substances. The compounds are thin-layer chromatographically uniform, using as the flow agent a mixture of hexane and acetone (2:1), developed with a 3% palladium chloride solution. I
The dichlorophenols of the Formula II, used as starting compounds, may. be prepared by the. following method: Y
A suitable, tetrachlorobenzene, such as 1,2,3,4-tetrachlorobenzene, preferably in slight stoichiometric excess,
is reacted at moderately elevated temperatures with a mercaptan of the formula R SH (IV) wherein R has the same meanings as in Formula I, and with a molar equivalent of an alkali metal hydroxide in aqueous-methanolic solution. Upon working up the reaction mixture in the usual manner, a good yield of the principal reaction product, i.e. the corresponding 1-(R mercapto)-2,3,6-trichlorobenzene, is obtained. In addition, the isomeric secondary reaction product, i.e. the corresponding l-(R -mercapto)-2,3,4-trich1orobenzene, canbe isolated from the reaction mixture. These compounds are then hydrolized with aqueous-methanolic alkali metal hydroxide; for instance, hydrolysis of a 1-(R -mercapto)- 2,3,6-trichlorobenzene produces high yields of a 2-(R mercapto)-3,4-dichlorophenol as the principal product and a 2-(R -mercapto)-3,6-dichlorophenol as a secondary reaction product. The isomers may be separated in customary fashion, such as by fractionaldistillation.
In analogous manner, othertetrachlorobenzenes may be reacted in like fashion, for instance, 1,2,4,5-tetrachlorobenzene produces good yields of a 4-(R -mercapto)-2,5- dichlorophenol by way of the corresponding intermediate 1-(Rg-1I16I'C3Pt0) -2,4,5-trichlorobenzene.
- The conversion of a dichloro-(R -mercapto)-phenol into the corresponding R -sulfinyl compound by oxidation may be effected in customary fashion with hydrogen peroxide in glacial acetic acid.
The following examples further illustrate the present invention and will enable others skilled in the art to understand it more completely. It should be understood, however, that the invention is not limited solely to the particular examples given below.
EXAMPLE 1 (a) 0,0-diethyl-O-( 2,5 -dichloro-4-methylsulfinylphenyl)-thionophosphate (mol. weight 377.26)
24.7 gm. (0.1 mol) of sodium 2,5-dich1oro-4-methylsulfinylphenolate (M.P. of the phenol 210 C.) were stirred in m1. of methyl isobutyl ketone with 20.8 gm. (0.11 mol) of 0,0 diethyl-thionophosphoric acid chloride for three hours at C. Then, the solvent was distilled oif, the residue was dissolved in methylene chloride, and the-solution was extracted with water, with 2 N sodium hydroxide solution and again withwater and dried over sodium sulfate. The methylene chloride was distilledofi, and the residue was heated for half an hour on a boiling water bath under an oil pump vacuum.
Yield: 35.7 gm. of theory), M.P. 5859 C., of
' thecompound C2H5O \C I 1 1 ,l q 0211.0 0.-so-om Analysis:
P calc.: 8.22%; found: 8.14% Scale: l7,. 03.%;found: 16.94%-
,Cl calc.: 18.81%; found:-19.00%,
3 Analysis:
Pcalc.: 8.87%; found: 8.72% Scalc.: 18.36%;found: 18.30% Cl calc.: 20.26%; found: 20.10%
(c) O-methyl-O-(2,5-dichloro 4 methylsulfinylphenyl)-methyl-thionophosphonate of the formula Analysis:
P calc.: 9.30%; found: 9.40% Sca1c.: 19.28%;found: 19.20% Cl'calc.: 21.28%; found: 21.34%
(d) O-ethyl-O- (2,5 dichloro 4 methylsulfinylphenyl)-methyl-thionophosphonate from sodium 2,5-dichloro- 4-methylsulfinylphenolate and methyl-thionophosphonic acid ethyl ester chloride: Yield: gm. (87% of theory); mol. weight 347.24.
Analysis:
Pcalc.: 8.93%;found: 8.76% Scalc.: 18.50%;found: 18.28% Cl calc.: 20.42%; found: 20.20%
(e) O-ethyl-O-(2,5 dichloro 4 methylsulfinylphenyl)-ethyl-thionophosphonate from sodium 2,5-dichloro-4- methylsulfinylphenolate and ethyl-thionophosphonic acid ethyl ester chloride: Yield: 30 gm. (83% of theory); mol. weight 361.26.
Analysis:
Pcalc.: 8.56%; found: 8.50% Scalc.: 17.78%; found: 17.92% Cl calc.: 19.64%;found: 19.47%
(f) O-n-propyl-O-(2,5 dichloro-4-methylsulfinylphenyl)-methyl-thionophosphonate from sodium 2,5-dichloro- 4-methylsulfinylphenolate and methyl-thionophosphoric acid n-propyl ester chloride: Yield: 29 gm. (82% of theory); mol. weight 361.26.
Analysis:
Pcalc.: 8.56%; found: 8.47% Scalc.: 17.78%;found: 17.86% Cl calc.: 19.64% ;found: 19.80%
(h) O-ethyl-Q-(2,5 dichloro 4 methylsulfinylphenyl)-phenyl-thionophosphonate of the formula from sodium 2,5-dichloro-4-methy1-sulfinylphenolate and phenyl-thionophosphonic acid ethyl ester chloride: Yield: 33 gm. (82% of theory); mol. weight 409.29.
Analysis:
P calc.: 7.58; found: 7.42% S calc.: 15.68%; found: 15.60% Clca1c.: 17.35%;found: 17.30%
4 EXAMPLE 2 0,0-dimethyl-O-(2-methylmercapto-3,4-dichlorophenyl -thionophosph ate (a) l-rnethylmercapto-2,3,6-trichlorobenzene.-A mixture of 2462 grn. (11.4 mol) of 1,2,3,4-tetrachlorobenzene, 6000 ml. of methanol, 855 gm. of aqueous 47% technical grade sodium hydroxide solution (10 mol) and 480 gm. (10 mol) of methylmercaptan was heated at 130 C. for 20 hours in an autoclave equipped with a stirrer. After cooling, the sodium chloride formed by the reaction was removed, the methanol was distilled off, and the reaction product was distilled in vacuo in a fractional distillation column. After the unreacted 1,2,3,4-tetrachlorobenzene had distilled off, 1420 gm. (62.5% of theory) of l-methylmercapto-2,3,6-trichlorobenzene distilled over at -96 C./0.3 mm. Hg. From the residue (400 gm.), 1-methylmercapto-2,3,4-trichlorobenzene and 1,2-methylmercapto-3,4-dichlorobenzene may be isolated.
(b) 2-methylmercapto-3,4-dichlorophenoL-A mixture of 113.5 gm. (0.5 mol) of 1-methylmercapto-2,3,6-trichlorobenzene, 42 gm. of sodium hydroxide and 400 ml. of methanol was heated at C. for twelve hours in an autoclave equipped with a stirrer. After cooling, the methanol was distilled off, the phenolate was dissolved by addition of water, and the aqueous solution was extracted with toluene. In order to liberate the phenol, the aqueous phase was acidified. Yield: 85 gm. (81.3% of theory). The reaction product was a mixture of 76% of 1-methylmercapto-3,4-dichlorophenol and 24% of l-methylmercapto-3,6-dichlorophenol, as verified by NMR-spectrum and gas chromatographical analysis. For separation of the isomers a fractionating column was used.
(c) 0,0-dimethylO (Z-methylmercapto 3,4 dichlorophenyl) thionophosphate (mol. Weight 333.2l).ll5 gm. of sodium 2-methylmercapto-3,4-dichlorophenolate were dissolved in 700 ml. of methyl isobutyl ketone, and the solution was heated to 70-80 C. 90 gm. of 0,0-dimethylthiophosphoric acid chloride were added dropwise, and the mixture was allowed to stand at this temperature for three hours. After cooling, the reaction solution was filtered, and the solvent was distilled off. The residue was dissolved in methylenechloride, and the solution was washed with water. The methylene chloride was distilled from the organic phase, yielding gm. (91% of theory) of the crude ester, B.P. 143-145 C./0.1 mm. Hg, of the formula CHaO S \P% CH S (Ill cao O C. Analysis:
P calc.: 9.30%; found: 9.20% 'S calc.: 19.28%; found: 19.46% Cl calc.: 21.28%; found: 21.30%
EXAMPLE 3 Analysis:
P calc.: 8.56%; found: 8.62% S calc.: 17.78%;found: 17.80% Cl calc.: 19.64%;found: 19.60%
EXAMPLE 4 Using a procedure analogous to that described in Example 2(c), 0,0-diethyl O (Z-methylmercapto-3,6-dichlorophenyl)-thionophosphate (mol. weight 361.26), B.P. C. at 0.1 mm. Hg, was prepared from equimolar quantities of 0,0-diethyl-thionophosphoric acid chloride and sodium 2-methylmercapto-3,6-dichlorophenolate. Yield: 93.7% of theory.
Analysis:
P calc.: 8.56%; found: 8.62% S calc.: 17.78%; found: 17.88% Cl calc.: 19.64%;found: 19.60%
EXAMPLE 5 0,0 diethyl-O-(2-methylmercapto-3,4-dichlorophenyl)- thionophosphate and 0,0-diethyl-O-(2-methylmercapto- 3,6-dichlorophenyl)-thionophosphate in the ratio 76:24
(a) The phenol mixture obtained according to Example 2(b) was reacted in phenolate-form with 0,0-diethylthionophosphoric acid chloride and worked up as described in Example 2(c). Yield: 94% of theory; B.P. 152-155 C. at 0.1 mm. Hg.
Analogous to Example 2(c) the following compounds were also prepared:
(b) 0,0-dimethyl O (2-methy1sulfinyl-3,4-dichlorophenyl)-thionophosphate, an unstable oil, from sodium 2-methylsulfinyl-3,4-dichlorophenolate and 0,0-dimethylthionophosphoric acid chloride. Yield: 81% of theory.
(0) 0,0-diethyl O (2 methylsulfinyl-3,4-diohlorophenyl)-thionophosphate from sodium Z-methylsulfinyl- 3,4-dichlorophenolate and 0,0-diethylthionophosphoric acid chloride. Yield: 82% of theory.
(d) O-ethyl-O-(2-methylmercapto-3,4-dichlorophenyl)- ethylthionophosphonate from sodium 2-methylmercapto- 3,4-dichlorophenolate and O-ethyl-ethylthionophosphonic acid chloride. Yield: 84% of theory; mol. weight 345.26
Analysis:
P calc.: 8.98%; found: 9.00% Scalc.: 18.60%; found: 18.68% Cl calc.: 20.58%; found: 20.70%
Analysis:
P calc.: 7.89%; found: 8.03% Scalc.: 16.32%;found: 16.50% Cl calc.: 18.02%; found: 18.00%
2-methylsulfinyl-3,4-dichlorophenol was obtained from the corresponding Z-methylmercapto compound by oxidation with the molecular quantity of hydrogen peroxide in glacial acetic acid at 0 to 40 C. in conventional fashion. The phenol melted at 216-218 C.
EXAMPLE 6 (a) 0,0-diethyl-O-(2,5-dichloro-4-octylsulfinylphenyl)- thionophosphate (mol. weight 475.43)
34.7 gm. (0.10 mol) of sodium 2,5-dichloro-4-octylsulfinylphenolate were reacted in 70 ml. of methyl isobutyl ketone with 20.8 gm. (0.11 mol) or 0,0-diethylthionophosphoric acid chloride. The reaction mixture was stirred for three hours at 80 C., subsequently the solvent was distilled off, the residue dissolved in methylene chloride, and the solution was extracted with water, then with 2 N sodium hydroxide, then again with water. The organic phase was dried over sodium sulfate and evaporated, and the residue was heated for half an hour on a boiling water bath in an oil pump vacuum. Yield: 46 gm. (97% of theory).
Analysis:
P calc.: 6.52%; found: 6.48% Scalc.: 13.47%;found: 13.40% Cl calc.: 14.92%;found: 14.80%
(b) In analogous manner 0,0-diethyl-O-(2,5-dichloro- 4-butylsulfinylphenyl)-thionophosphonate (mol. weight 419.32) was prepared from sodium 2,5-dichloro-4-buty1 sulfinylphenolate (0.10 mol) and 0,0-diethyl-thionophosphoric acid chloride (0.11 mol). Yield: 40.0 gm. (95.5% of theory).
Analysis:
P calc.: 7.38%; found: 7.38%
S calc.: 15.23%;found: 15.10%
Cl calc.: 16.91%;found: 16.80%
EXAMPLE 7 (a) 0,0-diethyl-O-(2,5-dichloro-4-octylmercaptophenyl) thionophosphate (mol. weight 459.43)
32.4 gm. (0.10 mol) of 2,S-dichloro-4-octylmercaptophenol were dissolved in 20 ml. of 5 N sodium hydroxide. At 6070 C. 20.8 gm. (0.11 mol) of 0,0-diethyl-thionophosphoric acid chloride were added dropwise; subsequently, the mixture was stirred for three hours at C. The oily phase was taken up in methylene chloride, and the solution was washed with 2 N sodium hydroxide and then with water. The methylene chloride solution was dried over sodium sulfate, filtered and evaporated. The residue was heated on a boiling water bath in an oil pump vacuum for half an hour. Yield: 44.2 gm. (96.5% of theory).
Analysis: 7 P calc.: 6.76%; found: 6.60% Scalc.: 13.93%;found: 13.80% Cl calc.: 15.43%; found: 15.20%
In analogous manner the following compounds were also prepared:
(b) 0,0 diethyl-O-(2,5-dichloro-4-cyclohexylmercaptophenyl)-thionophosphate (mol. weight 429.26) of the formula (c) QO-dimethyl-O-(2,5-dichloro-4 cyclohexylmercaptophenyl)-thionophosphonate (mol. weight 401.21) from 2,5-dichloro 4 cyclohexylmercaptophenol (0.10 mol) and .0,0-dimethyl-thionophosphoric acid chloride (0.11 mol). Yield: 37.0 gm. (92.3% of theory).
Analysis: P calc.: 7.73%; found: 7.71% S calc.: 15.98%;found: 16.02% C1ca1c.: 17.73%';found:'17.60%
(d) -O,-O -diethyl-O-(2,5-dichloro 4 isopropylsulhnylphenyl)-thionophosphate (mol. weight 405.30) from 2,5- dichloro-4-isopropylsulfinylphenol (0.10 mol) and and 0,0-diethyl-thionophospholic acid chloride (0.11 mol). Yield: 36.8 gm. (90.8% of theory).
Analysis:
P calc.: 7.65%;found: 7.55% Scalc.: 15.80%;found: 15.45% Clca1c.: 17.52%; found: 17.30%
(e) 0,0-diethyl-O-(2,5-dichloro 4 butylsulfinylphenyl)-thionophosphate (mol. Weight 419.32) from 2,5-dichloro-4-butylsulfinylphenol (0.10 mol) and 0,0-diethylthionophosphoric acid chloride (0.11 mol). Yield: 39.5 gm. (94.2% of theory).
7 Analysis:
Pcalc.: 7.38%; found: 7.30% S calc.: 15.23%; found: 15.11% Cl calc.: 16.91%;found: 16.82%
(t) 0,0-dimethyl O (2,5-dichloro 4 butylsulfinylphenyl)-thionophosphate (mol. weight 391.27) from 2,5- dichloro-4-butylsulfinylphenol (0.10 mol) and 0,0-dimethyl-thionophosphoric acid chloride (0.11 mol). Yield: 37.1 gm. (94.9% of theory).
Analysis:
P calc.: 7.93%; found: 7.90% S calc.: 16.36%;found: 16.42% Cl calc.: 18.16%;found: 18.12%
O,O-diethyl-O-(3,4-dichloro 2 ethylmercaptophenyl)-thionophosphate (mol. weight 375.27) from 3,4- dichloro-2-ethylmercaptophenol (0.10 mol) and 0,0-diethyl-thionophosphoric acid chloride (0.11 mol). Yield: 35 gm. (93.9% of theory).
Analysis:
Pcalc.: 8.25%; found: 8.20% S calc.: 17.06%; found: 16.93% Cl calc.: 18.92%;found: 18.84%
(h) 0,0-diethyl O (3,4-dichloro 2 ethylsulfinylphenyl)-thionophosphate (mol. weight 391.27) from- 3,4- dichloro-2-ethylsulfinylphenol (0.10 mol) and 0,0-diethyl-thionophosphoric acid chloride (0.11 mol). Yield: 36.3 gm. (92.8% of theory).
Analysis:
P calc.: 7.93 found: 7.85% Scalc.: 16.37%;found: 16.33% Cl calc.: 18.15%; found: 18.07%
The novel compounds according to the present invention, that is, those embraced by the Formula I above, are highly effective broad-spectrum pesticides; they act not only as contact poisons but also as alimentary canal poisons. Their toxicity toward warm-blooded animals is extremely low. They are particularly eflective against red spider mites, aphids, weevils( Calandra), bedbugs (Cimex lectularius), roaches and the common housefly.
For pesticidal purposes the compounds according to the present invention are disseminated in the form of compositions consisting essentially of an inert carrier and a pesticidally efiective amount of the active ingredient. The inert carrier may be a gaseous substance, such as a propellant gas, or a liquid or solid substance. In addition, the compositions may comprise one or more other inert additives, such as emulsifiers, extenders and substances which increase the adherence of the compositions to surfaces or objects to which they may be applied. The compounds of the present invention may be the sole active pesticidal ingredients in the compositions, or they may be combined with other pesticidal agents. Examples of suitable forms of such compositions are, among others: dusting powders, suspensions, emulsions, solutions, aerosols, fumigating paper or powder, and ointments.
The preferred concentration of the compounds according to the present invention in such pesticidal compositions is from- 0.01 to 5% by weight.
The following examples illustrate various types of pesticidal compositions comprising a compound of the present invention as the active ingredient.
8 EXAMPLE 8 Emulsion 25 gm. of a compound of the Formula I, gm. of dimethylformamide and 5 gm. of nonylphenol polyglycol ether (emulsifier) were emulsified in an amount of water suflicient to make the concentration of the active ingredient from 0.01 to 0.2% -by weight, based on the overall weight of the emulsion.
This resulting pesticidal emulsion was highly effective against red spider mites, weevils, bedbugs and roaches.
EXAMPLE 9 Dusting powder.5 gm. of a compound of the Formula I, 94 gm. of talcum and 1 gm. of methylcellulose were admixed and milled until a homogenous powder was obtained.
The dusting powder, comprising 5% of the pesticidal ingredient, was also very effective in combatting red spider mites, weevils, bedbugs and roaches.
EXAMPLE 1 0 Suspension.-A mixture of 50 gm. of a compound of the Formula I, 9 gm. of lignin sulfonate (dispersing agent), 1 gm. of sodium tetrapropylene benzene sulfonate (wetting agent) and 40 gm. of kaolin was milled, and the resulting intimate mixture was suspended in an amount of water sufiicient to make the concentration of the active ingredient from 0.01 to 0.5% by weight, based on the overall weight of the suspension.
The resulting pesticidal suspension was also highly effective against red spider mite, weevils, bedbugs and roaches.
While the present invention has been illustrated with the aid of certain specific embodiments thereof, it will be readily apparent to others skilled in the art that the invention is not limited to these particular embodiments, and that various changes and modifications may be made without departing from the spirit of the invention or the scope of the appended claims.
I claim: 1. A compound of the formula 31 B/ \O-SOR3 wherein R is alkyl of 1 to 3 carbon atoms, R is alkyl of 1 to 3 carbon atoms, methoxy, ethoxy or phenyl, and R is alkyl of 1 to 4 carbon atoms. 2. 0,0 diethyl-O-(2,5-dichloro-4-methylsulfinylphenyl) -thionophosphate.
References Cited FOREIGN PATENTS 242,406 5/1959 Australia 260-949 CHARLES B. PARKER, Primary Examiner A. H. SUTTO, Assistant Examiner US. Cl. X.R. 424-21 6 zg gg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,639,5140 Dated February 1972 Inventor RICHARD SEHRING It is certified that error a and that said Letters Patent are Col. 1, line 19:
ppears in the above-identified patent hereby corrected as shown below:
Col. 3, line 65: "(2611 0" should read --'c H Signed and sealed this 18th day of July 1972.
(SEAL) Attest: I I I .FLETCHE'R JR. ROBERT GOTTSCHALK 22 22221 23 Officer Commissioner of Pate ts
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1643706 | 1967-12-04 | ||
DE19681643764 DE1643764A1 (en) | 1968-02-27 | 1968-02-27 | Pest repellants |
Publications (1)
Publication Number | Publication Date |
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US3639540A true US3639540A (en) | 1972-02-01 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US780870A Expired - Lifetime US3639540A (en) | 1967-12-04 | 1968-12-03 | Sulfinyl phenyl esters of thionophosphoric or thionophosphonic acids |
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Country | Link |
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US (1) | US3639540A (en) |
BE (1) | BE724928A (en) |
CH (1) | CH506247A (en) |
FR (1) | FR1601467A (en) |
GB (1) | GB1205099A (en) |
IL (1) | IL31222A0 (en) |
NL (1) | NL6817296A (en) |
-
1968
- 1968-12-02 CH CH1795468A patent/CH506247A/en not_active IP Right Cessation
- 1968-12-03 US US780870A patent/US3639540A/en not_active Expired - Lifetime
- 1968-12-03 NL NL6817296A patent/NL6817296A/xx unknown
- 1968-12-04 FR FR1601467D patent/FR1601467A/fr not_active Expired
- 1968-12-04 IL IL31222A patent/IL31222A0/en unknown
- 1968-12-04 GB GB57625/68A patent/GB1205099A/en not_active Expired
- 1968-12-04 BE BE724928D patent/BE724928A/xx unknown
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GB1205099A (en) | 1970-09-16 |
FR1601467A (en) | 1970-08-24 |
IL31222A0 (en) | 1969-02-27 |
CH506247A (en) | 1971-04-30 |
BE724928A (en) | 1969-06-04 |
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